EP4130197B1 - Flammhemmende zusammensetzung, flammhemmende kunstharzzusammensetzung und formkörper - Google Patents

Flammhemmende zusammensetzung, flammhemmende kunstharzzusammensetzung und formkörper

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Publication number
EP4130197B1
EP4130197B1 EP21779179.7A EP21779179A EP4130197B1 EP 4130197 B1 EP4130197 B1 EP 4130197B1 EP 21779179 A EP21779179 A EP 21779179A EP 4130197 B1 EP4130197 B1 EP 4130197B1
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EP
European Patent Office
Prior art keywords
flame
synthetic resin
flame retardant
mass
component
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Active
Application number
EP21779179.7A
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English (en)
French (fr)
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EP4130197A1 (de
EP4130197A4 (de
Inventor
Keisuke BANNO
Ayaka Mitsuhashi
Naoko Tanji
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Adeka Corp
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Adeka Corp
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Publication of EP4130197A4 publication Critical patent/EP4130197A4/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/529—Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the present invention relates to a flame retardant composition that can provide a flame-retardant synthetic resin composition (hereinafter, also simply referred to as "resin composition”) which has excellent flame retardance and which is excellent in shrinkage balance during molding, and a flame-retardant synthetic resin composition using the same and a molded body thereof.
  • resin composition a flame-retardant synthetic resin composition
  • flame retardants for synthetic resins
  • an intumescent-based flame retardant mainly containing a salt of polyphosphoric acid or pyrophosphoric acid and a nitrogen-containing compound is known as an excellent flame retardant that makes synthetic resins flame-retardant by forming a surface expansion layer (Intumescent) during combustion and suppressing diffusion of a decomposed product and/or heat transfer.
  • Such a flame retardant is described in, for example, Patent Document 1.
  • Patent Document 5 discloses a resin additive composition composed of a phosphoric acid ester compound, a thermoplastic resin composition containing the same, and a molded article thereof.
  • Patent Document 6 dislcoses a composition containing a cyclic organophosphate aluminium salt and sodium carboxylate, a thermoplastic resin composition that uses the same, and a molded article thereof.
  • Patent Document 7 dislcoses a synthetic resin composition including a phosphate ester compound as a crystallisation agent.
  • a problem is that, if the above flame retardant is compounded to a synthetic resin and injection molding is performed, the mold shrinkage factor in the MD direction (flow direction of the resin in a mold) is larger than the mold shrinkage factor in the TD direction (direction perpendicular to the MD direction).
  • a molded body containing the above flame retardant is changed in longitudinal and lateral balance in terms of mold shrinkage factor, as compared with a molded body not containing the above flame retardant, and a molded body having a shape as initially designed with a mold is difficult to obtain.
  • An object of the present invention for solving the above problems is to provide a flame retardant composition that can provide a flame-retardant synthetic resin composition excellent in flame retardance and in longitudinal and lateral balance in terms of mold shrinkage factor, and a flame-retardant synthetic resin composition using the same and a molded body thereof.
  • the flame retardant composition of the present invention is outlined in claim 1.
  • the molded body of the present invention is obtained by molding the above flame-retardant synthetic resin composition.
  • a flame retardant composition that can provide a flame-retardant synthetic resin composition excellent in flame retardance and in shrinkage balance during molding, and a flame-retardant synthetic resin composition using the same and a molded body thereof.
  • the present invention relates to a flame retardant composition, a flame-retardant synthetic resin composition and a molded body.
  • a flame retardant composition a flame-retardant synthetic resin composition
  • a molded body a flame-retardant synthetic resin composition
  • the flame retardant composition of the present invention essentially contains a phosphoric acid salt-based flame retardant as component (A) and one or more compounds each having a structure represented by general formula (1), as component (B).
  • Examples of the phosphoric acid compound used in the phosphoric acid salt-based flame retardant include, but not particularly limited to, various phosphoric acid compounds such as orthophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.
  • the polyphosphoric acid in the present invention means a so-called condensed phosphoric acid, and examples include linear polyphosphoric acid and cyclic polymetaphosphoric acid. The degree of condensation of the polyphosphoric acid is 3 or more.
  • aliphatic amine examples include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine.
  • a known treatment for an enhancement in water resistance for example, a treatment with a silane coupling agent or covering with a melamine resin may be applied to the phosphoric acid salt-based flame retardant, or a known foaming aid such as melamine, melamine cyanurate, or pentaerythritol may be added thereto.
  • phosphoric acid salt-based flame retardant examples include an orthophosphoric acid salt, a pyrophosphoric acid salt, and a polyphosphoric acid salt.
  • the orthophosphoric acid salt is not particularly limited, and examples thereof include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate, sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite and sodium hypophosphite, potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite and potassium hypophosphite, lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite and lithium hypophosphite, barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate and barium hypophosphi
  • the pyrophosphoric acid salt is not particularly limited, and examples thereof include ammonium pyrophosphate, piperazine pyrophosphate, melamine pyrophosphate, and aluminum pyrophosphate.
  • the polyphosphoric acid salt is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, and aluminum polyphosphate.
  • the phosphoric acid salt-based flame retardant can be used singly or in combination of two or more kinds thereof.
  • the phosphoric acid salt-based flame retardant containing component (A) contains components (A-1), and (A-2) from the viewpoints of flame retardance and heat resistance.
  • the phosphoric acid salt-based flame retardant containing component (A) preferably contains component (A-3) from the viewpoints of flame retardance and heat resistance.
  • Component (A-1) one or more melamine salts selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate.
  • Component (A-2) one or more piperazine salts selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate.
  • Component (A-3) one or more ammonium salts selected from the group consisting of ammonium orthophosphate, ammonium pyrophosphate and ammonium polyphosphate.
  • the melamine salt used as component (A-1) in component (A) in the present invention is selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate, and these salts may be used singly or as a mixture thereof.
  • melamine pyrophosphate or melamine polyphosphate is preferable and melamine pyrophosphate is particularly preferable from the viewpoints of flame retardance, handleability and storage stability.
  • a higher content rate of melamine pyrophosphate is more preferable.
  • the piperazine salt used as component (A-2) in component (A) in the present invention is selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate, and these salts may be used singly or as a mixture thereof.
  • piperazine pyrophosphate is preferable from the viewpoints of flame retardance, handleability and storage stability, and when a mixture is adopted, a higher content rate of piperazine pyrophosphate is more preferable.
  • the piperazine salt used as component (A-2) in the present invention is preferably piperazine pyrophosphate or piperazine polyphosphate obtained by heating and condensing piperazine diphosphate, and particularly preferably piperazine pyrophosphate.
  • ammonium salt used as component (A-3) in component (A) in the present invention is selected from the group consisting of ammonium orthophosphate, ammonium pyrophosphate and ammonium polyphosphate, and these salts may be used singly or as a mixture thereof.
  • Component (A) in the present invention contains components (A-1) and (A-2) from the viewpoint of flame retardance.
  • the content rate between components (A-1) and (A-2) is 30:70 to 45:55 in terms of the mass ratio between the components (A-1) and (A-2), from the viewpoint of flame retardance.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 5 represents a direct bond or an alkanediyl group having 1 to 4 carbon atoms
  • M 1 represents lithium or aluminium
  • n is 1 and m is 0 when M 1 represents lithium
  • n is 1, 2 or 3 and m is an integer represented by 3 - n when M 1 represents aluminum.
  • Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, and a tert-octyl group.
  • an alkyl group having 1 to 5 carbon atoms is preferable, and a tert-butyl group is particularly preferable, from the viewpoint of the effects of the present invention.
  • Examples of the alkanediyl group having 1 to 4 carbon atoms represented by R 5 in the general formula (1) include a methanediyl group, an ethan-1,1-diyl group, a propan-1,1-diyl group, a propan-2,2-diyl group, a butan-1,1-diyl group, and a butan-2,2-diyl group.
  • a methanediyl group or an ethan-1,1-diyl group is preferable from the viewpoint of the effects of the present invention.
  • Component (B) in the present invention can be used singly or in combination of two or more kinds thereof.
  • component (B) in the present invention in which M 1 in the general formula (1) is lithium or aluminium, include the following Compounds No. 1 to No. 6. It is noted that component (B) in the present invention is not limited to these compounds.
  • M 1 in the general formula (1) is aluminum
  • component (B) in the present invention is not limited to these compounds.
  • Component (B) in the present invention has the effect of allowing the ratio in longitudinal and lateral balance between respective mold shrinkage factors in a flow direction (MD direction) of a resin and in a direction (TD direction) perpendicular to the flow direction during injection molding of the resin composition to be close to 1, and thus suppressing warpage and deformation of a molded body.
  • the content of component (B) in the flame retardant composition of the present invention is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, still more preferably 0.05 to 1 part by mass based on 100 parts by mass of component (A), from the viewpoints of flame retardance, and shrinkage balance during molding.
  • the flame retardant composition of the present invention preferably contains at least one selected from a filler, a fatty acid metal salt and a hydrotalcite compound, as component (C), from the viewpoint that the effects of the present invention are more enhanced.
  • the filler can include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, a glass powder, glass fiber, clay, dolomite, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate and hydrotalcite, and the filler can be used by appropriately selecting the particle size, and the fiber diameter, the fiber length and the aspect ratio in the case of a fibrous form. These may be used singly or in combination of two or more kinds thereof.
  • the filler can be used in the form of being surface-treated, if necessary.
  • fatty acid metal salt examples include a compound having a structure represented by the following general formula (2):
  • R 4 represents a group derived from a linear or branched aliphatic organic acid having 8 to 30 carbon atoms
  • M 2 represents a metal atom or Al(OH) 3-p
  • p represents an integer of 1 to 3.
  • fatty acid metal salt examples include metal salts of saturated fatty acids such as caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, and 12-hydroxystearic acid, metal salts of linear unsaturated fatty acids such as 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, ⁇ -linolenic acid, linolic acid, ⁇ -linolenic acid, stearidonic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, e
  • Examples of the metal atom represented by M 2 in the general formula (2) include an alkali metal atom, an alkali earth metal atom, a transition metal atom, and a base metal atom.
  • An alkali metal atom such as sodium, lithium or potassium is preferable in the composition of the present invention because the effects of the present invention are remarkable.
  • the amount thereof compounded is preferably adjusted so as to be 0.0005 to 5 parts by mass, in particular, 0.001 to 3 parts by mass based on 100 parts by mass of the synthetic resin.
  • x1 and x2 respectively represent numbers satisfying conditions represented by the following expressions, 0 ⁇ x 2 / x 1 ⁇ 10,2 ⁇ x 1 + x 2 ⁇ 20 in which q represents 0 or a positive number.
  • q represents 0 or a positive number.
  • a r- represents an r-valent anion
  • q represents 0 or a positive number
  • the carbonate anion in such a hydrotalcite compound may be partially substituted with other anion.
  • the hydrotalcite compound may be obtained by dehydrating crystal water, or may be covered with, for example, a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an oleic acid alkali metal salt, an organic sulfonic acid metal salt such as a dodecylbenzenesulfonic acid alkali metal salt, a higher fatty acid amide, a higher fatty acid ester, or wax.
  • a higher fatty acid such as stearic acid
  • a higher fatty acid metal salt such as an oleic acid alkali metal salt
  • an organic sulfonic acid metal salt such as a dodecylbenzenesulfonic acid alkali metal salt
  • a higher fatty acid amide such as a higher fatty acid amide
  • a higher fatty acid ester or wax.
  • the hydrotalcite compound may be a natural product or a synthetic product.
  • Examples of the synthesis method of the hydrotalcite compound include known methods described in, for example, JP-S46-2280B , JP-S50-30039B , JP-S51-29129B , JP-H3-36839B , JP-S61-174270A , and JP-H5-179052A .
  • the hydrotalcite compound can be used without any limitations on the crystal structure, the crystal particle, and the like thereof.
  • the compound may be used singly or in combination of two or more kinds thereof.
  • the amount thereof compounded is preferably adjusted so as to be 0.001 to 5 parts by mass, in particular, 0.01 to 3 parts by mass based on 100 parts by mass of the synthetic resin.
  • the zinc oxide functions as a flame retardant aid.
  • the zinc oxide may be surface-treated.
  • the zinc oxide here used can be a commercially available product, and examples thereof include zinc oxide of JIS 1 grade (manufactured by MITSUI MINING & SMELTING CO., LTD.), zinc oxide partially coated (manufactured by MITSUI MINING & SMELTING CO., LTD.), NANOFINE 50 (ultrafine particulate zinc oxide having an average particle size of 0.02 ⁇ m: manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.), and NANOFINE K (ultrafine particulate zinc oxide coated with zinc silicate, having an average particle size of 0.02 ⁇ m: manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.).
  • the content of the zinc oxide as component (D) in the flame retardant composition of the present invention is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, further preferably 1 to 5 parts by mass based on 100 parts by mass of component (A) from the viewpoint of flame retardance.
  • the content of the zinc oxide is set to 0.01 parts by mass or more, and therefore flame retardance is more favorable.
  • the content of the zinc oxide is set to 30 parts by mass or less, and therefore an adverse effect on processability hardly occurs.
  • the flame retardant composition of the present invention preferably further contains at least one selected from the group consisting of silicone oil, an epoxy-based coupling agent and a lubricant, as component (E).
  • the flame retardant composition of the present invention contains component (E), a flame retardant powder can be inhibited from being aggregated, and an enhancement in storage stability, an enhancement in dispersibility in the synthetic resin, and an enhancement in flame retardance can be expected.
  • silicone oil examples include dimethylsilicone oil where all side chains and terminals of polysiloxane are methyl groups, methyl phenyl silicone oil where side chains and terminals of polysiloxane are methyl groups and some of the side chains are phenyl groups, methyl hydrogen silicone oil where side chains and terminals of polysiloxane are methyl groups and some of the side chains are hydrogen, and copolymers thereof, and amine-modified, epoxy-modified, alicyclic epoxy-modified, carboxyl-modified, carbinol-modified, mercapto-modified, polyether-modified, long-chain alkyl-modified, fluoroalkyl-modified, higher fatty acid ester-modified, higher fatty acid amide-modified, silanol-modified, diol-modified, phenol-modified and/or aralkyl-modified modified-silicone oil(s) can be used where organic groups are introduced into some of side chains and/or terminals
  • silicone oil examples include dimethylsilicone oils such as KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-965 (manufactured by Shin-Etsu Chemical Co., Ltd.) and KF-968 (manufactured by Shin-Etsu Chemical Co., Ltd.), methyl hydrogen silicone oils such as KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-9901 (Shin-Etsu Chemical Co., Ltd.), HMS-151 (manufactured by Gelest Inc.), HMS-071 (manufactured by Gelest Inc.), HMS-301 (manufactured by Gelest Inc.) and DMS-H21 (manufactured by Gelest Inc.), methyl phenyl silicone oils such as KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-53 (manufactured by Shin-Ets, Ltd
  • Methyl hydrogen silicone oils are preferable in the flame retardant composition of the present invention in that a flame retardant powder is prevented from being aggregated and storage stability and dispersibility in the synthetic resin can be enhanced.
  • the content of component (E) in the flame retardant composition of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass based on 100 parts by mass of component (A) from the viewpoint that the effect by containing component (E) is effectively exerted.
  • Examples of the phosphorus-based antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis(dipropylene glycol)triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctyl phenyl phosphite, diphenyl tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropylene glycol)phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis(tridecyl)phosphite, tris(tridecyl)phosphite, di
  • the content of the phosphorus-based antioxidant in the flame retardant composition of the present invention can be in a range that does not impair any effects of the present invention, and is preferably in an amount of 0.01 to 1 part by mass, more preferably in an amount of 0.03 to 0.8 parts by mass based on 100 parts by mass of the synthetic resin included in the resin composition containing the flame retardant composition of the present invention.
  • the content of the thioether-based antioxidant in the flame retardant composition of the present invention can be in a range that does not impair any effects of the present invention, and is preferably in an amount of 0.001 to 10 parts by mass, more preferably in an amount of 0.005 to 5 parts by mass based on 100 parts by mass of the synthetic resin included in the resin composition containing the flame retardant composition of the present invention.
  • hindered amine-based light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)/bis(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)/di(tridecyl)-1
  • the content of the ultraviolet absorber in the flame retardant composition of the present invention can be in a range that does not impair any effects of the present invention, and is preferably in an amount of 0.001 to 10 parts by mass, more preferably in an amount of 0.005 to 1 part by mass based on 100 parts by mass of the synthetic resin included in the resin composition containing the flame retardant composition of the present invention.
  • Preferable examples include polyester-based plasticizers, phthalic acid-based plasticizers, trimellitic acid-based plasticizers, adipic acid-based plasticizers, sebacic acid-based plasticizers, and epoxy-based plasticizers.
  • plasticizers may be used singly or in combination of two or more kinds thereof.
  • the content of the plasticizer in the flame retardant composition of the present invention can be in a range that does not impair any effects of the present invention, and is preferably in an amount of 1 to 90 parts by mass, more preferably in an amount of 10 to 80 parts by mass based on 100 parts by mass of the synthetic resin included in the resin composition containing the flame retardant composition of the present invention.
  • the content of the crystal nucleating agent in the flame retardant composition of the present invention can be in a range that does not impair any effects of the present invention, and is preferably in an amount of 0.001 to 10 parts by mass, more preferably in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of the synthetic resin included in the resin composition containing the flame retardant composition of the present invention.
  • Examples of the flame retardant other than component (A) in the present invention include aromatic phosphates such as triphenyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene)-4,1-phenylenetetraphenyl diphosphate and 1,3-phenylene tetrakis(2,6-dimethylphenyl)phosphate, trade names "ADK STAB FP-500", “ADK STAB FP-600", “ADK STAB FP-800” and "ADK STAB FP-900L” manufactured by ADEKA CORPORATION, phosphonates such as divinyl phenylphosphonate, diallyl phenylphosphonate and (1-butenyl) phenylphosphonate, pho
  • the content of the flame retardant other than component (A) in the present invention, in the flame retardant composition of the present invention, can be in a range that does not impair any effects of the present invention, and is preferably in an amount of 1 to 90 parts by mass, more preferably in an amount of 3 to 80 parts by mass based on 100 parts by mass of the synthetic resin included in the resin composition containing the flame retardant composition of the present invention.
  • polyhydric alcohol compounds one or more selected from the group consisting of pentaerythritol, pentaerythritols such as dipentaerythritol, tripentaerythritol and polypentaerythritol, and respective condensates of such pentaerythritols are preferable, respective condensates of dipentaerythritol and pentaerythritol are particularly preferable, and dipentaerythritol is most preferable.
  • THEIC and sorbitol can also be suitably used.
  • Such flame retardant aids may be used singly or in combination of two or more kinds thereof.
  • the content of the flame retardant aid in the flame retardant composition of the present invention can be in a range that does not impair any effects of the present invention, and is preferably in an amount of 0.01 to 20 parts by mass, more preferably in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the synthetic resin included in the resin composition containing the flame retardant composition of the present invention.
  • Examples of the dripping inhibitor include a fluorine-based dripping inhibitor, silicone rubber, and lamellar silicate.
  • Examples of the fluorine-based dripping inhibitor include fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride and polyhexafluoropropylene, perfluoroalkanesulfonic acid alkali metal salt compounds such as a perfluoromethanesulfonic acid sodium salt, a perfluoro-n-butanesulfonic acid potassium salt, a perfluoro-t-butanesulfonic acid potassium salt, a perfluorooctanesulfonic acid sodium salt and a perfluoro-2-ethylhexanesulfonic acid calcium salt, or perfluoroalkanesulfonic acid alkali earth metal salts.
  • lamellar silicate examples include smectite-based clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite and non-tronite, vermiculite, halloysite, swellable mica, and talc, and one in which an organic cation, a quaternary ammonium cation or a phosphonium cation is intercalated may be adopted.
  • dripping inhibitors may be used singly or in combination of two or more kinds thereof.
  • a fluorine-based dripping inhibitor is preferable and polytetrafluoroethylene is most preferable from the viewpoint of dripping inhibition properties.
  • the acrylic processing aid here used can be obtained by polymerizing one (meth)acrylate or copolymerizing two or more kinds thereof.
  • the (meth)acrylate to be polymerized or copolymerized include (meth)acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, isobutyl acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate and tridecyl methacrylate.
  • Examples include, in addition to the above, (meth)acrylic acids, and
  • the content of the acrylic processing aid in the flame retardant composition of the present invention can be in a range that does not impair any effects of the present invention, and is preferably in an amount of 0.01 to 10 parts by mass, more preferably in an amount of 0.03 to 1 part by mass based on 100 parts by mass of the synthetic resin included in the resin composition containing the flame retardant composition of the present invention.
  • the content of the antistatic agent in the flame retardant composition of the present invention can be in a range that does not impair any effects of the present invention, and is preferably in an amount of 0.01 to 20 parts by mass, more preferably in an amount of 0.03 to 10 parts by mass based on 100 parts by mass of the synthetic resin included in the resin composition containing the flame retardant composition of the present invention.
  • a commercially available pigment can be used as the pigment, and examples thereof include Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, and 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, and 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147
  • the content of the pigment in the flame retardant composition of the present invention can be in a range that does not impair any effects of the present invention, and is preferably in an amount of 0.001 to 5 parts by mass, more preferably in an amount of 0.003 to 3 parts by mass based on 100 parts by mass of the synthetic resin included in the resin composition containing the flame retardant composition of the present invention.
  • the dye examples include an azo dye, an anthraquinone dye, an indigoid dye, a triarylmethane dye, a xanthene dye, an alizarin dye, an acridine dye, a stilbene dye, a thiazole dye, a naphthol dye, a quinoline dye, a nitro dye, an indamine dye, an oxazine dye, a phthalocyanine dye, and a cyanine dye.
  • Such dyes may be used singly or in combination of two or more kinds thereof.
  • the content of the dye in the flame retardant composition of the present invention can be in a range that does not impair any effects of the present invention, and is preferably in an amount of 0.001 to 5 parts by mass, more preferably in an amount of 0.003 to 3 parts by mass based on 100 parts by mass of the synthetic resin included in the resin composition containing the flame retardant composition of the present invention.
  • any other additive(s) for use in a common synthetic resin for example, a crosslinker, an anti-fogging agent, a plate-out inhibitor, a surface treatment agent, a fluorescent agent, a mildew-proofing agent, a fungicide, a foaming agent, a metal deactivator, a release agent, and/or a processing aid other than the acrylic processing aid may be, if necessary, compounded in the flame retardant composition of the present invention, as long as the effects of the present invention are not remarkably impaired.
  • a component may be compounded in the flame retardant composition of the present invention, in advance, or may be compounded in preparation of the flame-retardant synthetic resin composition as described below.
  • component (A) and component (B), and, if necessary, any other component may be mixed, and any of various mixing machines can be used in the mixing. Heating may be made during the mixing.
  • a usable mixing machine include a tumbler mixer, a Henschel mixer, a ribbon blender, a V-type mixing machine, a W-type mixing machine, a super mixer, and a Nauta mixer.
  • the content of the flame retardant composition in the flame-retardant synthetic resin composition of the present invention is preferably in an amount of 10 to 400 parts by mass, more preferably 10 to 300 parts by mass, further preferably 10 to 150 parts by mass, particularly preferably 20 to 120 parts by mass based on 100 parts by mass of the synthetic resin.
  • the content of the flame retardant composition based on 100 parts by mass of the synthetic resin is 10 parts by mass or more and thus sufficient flame retardance can be exhibited, and the content is 400 parts by mass or less and thus original physical properties of the resin are not impaired.
  • the pellet obtained by the above procedure was used, and was subjected to injection molding by an injection molding machine (EC60NII-1.5A; manufactured by Toshiba Machine Co., Ltd.) in the following conditions, to produce a test piece.
  • an injection molding machine EC60NII-1.5A; manufactured by Toshiba Machine Co., Ltd.
  • test piece was left to still stand in a thermostat at 23°C and at a humidity of 50% for 48 hours, thereafter each of the lengths in the MD direction and the TD direction thereof was measured in terms of dimension at three points, and the respective average values were defined as the dimension (MD 1 ) in the MD direction and the dimension (TD 1 ) in the TD direction of the test piece.
  • An image measurement machine "Quick Vision ELF" manufactured by Mitutoyo Corporation was used for such length measurement.
  • the respective shrinkage factors ⁇ MD and ⁇ TD of the base resin (Comparative Example 1) not containing the flame retardant composition of the present invention were defined as ⁇ MD B and ⁇ TD B .
  • the numerical value ⁇ TD/ ⁇ MD of the shrinkage isotropy obtained was normalized under the assumption that the numerical value ⁇ TD B / ⁇ MD B of the shrinkage isotropy of the base resin (Comparative Example 1) not containing the flame retardant composition of the present invention was 1.
  • the numerical value normalized is represented by ( ⁇ TD/ ⁇ MD)/( ⁇ TD B / ⁇ MD B ).
  • each composition of Examples 1 to 8 while maintained any evaluation rank of flame retardance, achieved values close to 1 as the ratio ( ⁇ TD/ ⁇ TD B ) of the shrinkage factor ⁇ TD relative to that of the base resin and the ratio (( ⁇ TD/ ⁇ MD)/( ⁇ TD B / ⁇ MD B )) of ⁇ TD/ ⁇ MD relative to that of the base resin, as compared with each composition (Comparative Examples 2 to 4) containing no component (B), and was favorable in longitudinal and lateral balance in terms of mold shrinkage factor during injection molding.
  • compositions (Comparative Examples 1 and 5 to 7) containing no component (A) were rated as NR in terms of evaluation rank in the flame retardance test, and resulted in flame retardance impaired as compared with each composition of Examples.

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Claims (6)

  1. Flammschutzmittelzusammensetzung, umfassend 0,005 bis 5 Masseteile der folgenden Komponente (B) auf Grundlage von 100 Masseteilen der folgenden Komponente (A), wobei Komponente (A) ein auf Phosphorsäuresalz basierendes Flammschutzmittel ist und
    Komponente (B) eine oder mehrere Verbindungen mit einer Struktur ist, die durch die folgende allgemeine Formel (1) dargestellt ist:
    wobei R1, R2, R3 und R4 jeweils unabhängig voneinander ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 8 Kohlenstoffatomen darstellen,
    R5 eine direkte Bindung oder eine Alkandiylgruppe mit 1 bis 4 Kohlenstoffatomen darstellt,
    M1 Lithium oder Aluminium darstellt,
    n 1 ist und m 0 ist, wenn M1 Lithium darstellt, und
    n 1, 2 oder 3 ist und m eine ganze Zahl ist, die durch 3 - n dargestellt wird, wenn M1 Aluminium darstellt, wobei die Komponente (A) die Komponenten (A-1) und (A-2) enthält:
    Komponente (A-1): ein oder mehrere Melaminsalze, ausgewählt aus der Gruppe, bestehend aus Melaminorthophosphat, Melaminpyrophosphat und Melaminpolyphosphat;
    Komponente (A-2): ein oder mehrere Piperazinsalze, ausgewählt aus der Gruppe, bestehend aus Piperazinorthophosphat, Piperazinpyrophosphat und Piperazinpolyphosphat, und das Gehaltsverhältnis (Massenverhältnis) zwischen den Komponenten (A-1) und (A-2) 30 : 70 bis 45 : 55 beträgt.
  2. Flammschutzmittelzusammensetzung nach Anspruch 1, die ferner als Komponente (C) wenigstens einen umfasst, der aus einem Füllstoff, einem Fettsäuremetallsalz und einer Hydrotalcitverbindung ausgewählt ist.
  3. Flammschutzmittelzusammensetzung nach Anspruch 2, wobei das Fettsäuremetallsalz eine Verbindung mit einer Struktur ist, die durch die folgende allgemeine Formel (2) dargestellt wird: wobei R4 eine Gruppe darstellt, die von einer linearen oder verzweigten aliphatischen organischen Säure mit 8 bis 30 Kohlenstoffatomen abgeleitet ist, M2 ein Metallatom oder Al(OH)3-p darstellt und p eine ganze Zahl von 1 bis 3 darstellt.
  4. Flammschutzmittelzusammensetzung nach Anspruch 1, ferner umfassend 0,01 bis 5 Masseteile von wenigstens einem, ausgewählt aus der Gruppe, bestehend aus Silikonöl, einem epoxidharzbasierten Kupplungsmittel und einem Schmiermittel, auf Grundlage von 100 Masseteilen der Komponente (A), als Komponente (E).
  5. Flammenschutzmittelkunstharzzusammensetzung, umfassend ein Kunstharz und die Flammschutzmittelzusammensetzung nach Anspruch 1, und die die durch die folgenden Ausdrücke (i) und (ii) dargestellten Beziehungen erfüllt: 0 , 935 ≤ ΔTD / Δ TD B ≤ 1 , 065 0 , 860 ≤ ΔTD / ΔMD / Δ TD B / Δ MD B ≤ 1 , 140 , wobei in den Ausdrücken ΔMD ein Schrumpfungsfaktor in einer MD-Richtung als eine Fließrichtung eines Harzes in einer Formkavität während des Spritzgießens eines Formkörpers ist, der durch Spritzgießen der Flammenschutzmittelkunstharzzusammensetzung erhalten wurde, ΔTD ein Schrumpfungsfaktor in einer TD-Richtung als eine Richtung senkrecht zu der MD-Richtung des Formkörpers ist, der durch Spritzgießen der Flammenschutzmittelkunstharzzusammensetzung erhalten wurde, ΔMDB ein Schrumpfungsfaktor in der MD-Richtung eines Formkörpers ist, der durch Spritzgießen einer Kunstharzzusammensetzung mit einem Zusammensetzungsverhältnis erhalten wurde, bei dem die Flammenschutzmittelzusammensetzung aus der Flammenschutzmittelkunstharzzusammensetzung ausgeschlossen ist, und ΔTDB ein Schrumpfungsfaktor in der TD-Richtung des Formkörpers ist, der durch Spritzgießen der Kunstharzzusammensetzung erhalten wurde.
  6. Formkörper, der durch Formen der Flammenschutzmittelkunstharzzusammensetzung nach Anspruch 5 erhalten wird.
EP21779179.7A 2020-03-31 2021-03-31 Flammhemmende zusammensetzung, flammhemmende kunstharzzusammensetzung und formkörper Active EP4130197B1 (de)

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WO2004000973A1 (ja) 2002-06-24 2003-12-31 Asahi Denka Co., Ltd. 難燃剤組成物及び該組成物を含有した難燃性樹脂組成物
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